金属Fe-Mg混合粉末对土壤中多氯联苯的降解作用研究
摘要
多氯联苯(polychlorinated biphenyls, PCBs)是目前国际上关注的12种持久性有机污染物(persistent organic pollutants, POPs)中最具有代表性的一类。由于其稳定的理化性质及疏水性,多氯联苯污染土壤的修复成为目前环境保护领域研究的热点之一。本文对零价金属铁镁混合粉末对多氯联苯污染土壤的修复效果进行了研究,取得了很好的结果。本文的主要工作如下：
1.研究了金属Fe-Mg混合粉末对土壤中多氯联苯的降解效果及其他反应条件对降解效果可能造成的影响。当金属混合粉末Fe和Mg的摩尔比为2：3,混合粉末添加量(wt)：污染土壤量(wt)=1：500,室内光及室温条件(20℃)下反应24h,污染土壤中多氯联苯的降解率达到98.10%。本研究中的降解方法还受到电解质溶液、反应时间、光照条件和温度等因素的影响。由实验结果可知,降解效率随着反应时间的延长不断提高,在反应开始的6h提高速率最快,到24h能达到98%以上；人工添加电解质溶液后,相同作用时间内获得的降解效率更高；直接光照有利于多氯联苯的降解,在反应最初的6-8h作用明显；在20℃-50℃的情况下,温度升高不利于多氯联苯的降解,20℃时,修复效果最好,降解效率为96.32%；Fe-Mg摩尔比在0.2-0.67的范围变化时,降解效率几乎没有变化；从2：3扩大到1：1时,降解率有所下降,1：1时的降解率为93.29%。
2.研究了金属Fe-Mg混合粉末对土壤中多氯联苯的降解机理。结果表明,在金属混合粉末作用下,多氯联苯脱氯降解,生成了两种新的产物：对异丙基甲苯和2,6-二(三甲基硅氧基)苯甲酸三甲基硅酯,其毒性均低于多氯联苯本身的毒性。
以上研究表明,零价金属铁镁混合粉末对多氯联苯污染土壤是一种有效的修复方法,为今后的PCBs污染土壤修复提供了较高的参考价值。
Polychlorinated biphenyl (PCB) is the most typical kind of 12 types of persistent organic pollutants (POPs) that people have always been paying attention to. Remediation of PCB-contaminated soil has been one of the hotspot researches for its extremely stable physical-chemical property. This paper has investigated the effect of zero-valent metallic mixed powder by iron and magnesium for repairing PCB-contaminated soils and has obtained good results. The main researches of the paper were as follows.
1. Investigating the degradation effect of PCB-contaminated soils by metallic mixed powder composed of iron and magnesium and reaction parameters that may have influences on removal efficiency. Removal rate of PCBs can be up to 98.10% in 24h under the conditions of Fe-Mg ration was 2:3 and power-soil ratio (wt%) was 1:500, in room with room temperature (20℃). The influences by electrolyte solution, reaction time, direct sunlight and temperature on the effect of remediation have also been studied. According to the experimental results, it can be seen that removal rate was increasing with the extension of reaction time and it could be up to 98% in 24h; addition of extra electrolyte solution could lead to better remediation effect in the same reaction time; direct sunlight has been proved to be helpful in the degradation process, especially in the first 6-8h; raising temperature was adverse to the degradation effect when temperature was ranging from 20℃to 50℃, it could get the highest removal rate 96.32% as temperature was controlled to 20℃. Ratio of Fe-Mg was ranging from 0.2-0.67 without any obvious change of removal efficiency, when it was raised from 0.67-1, removal rate has decreased and was 93.29% as the ratio was 1.
2. Investigating the mechanism of degradation. Result has indicated that two products were found after degradation process of PCBs, one was para-cymene, the other was trimethylsilyl 2,6-bis (trimethylsilyloxy) benzoate, toxicity of both were less than polychlorinated biphenyls.
Researches above demonstrated that zero-valent metallic mixed powder by iron and magnesium is an effective technique for remediation of PCB-contaminated soils and that, it provides a reference for remediation of PCB-contaminated soils in future.
1.研究了金属Fe-Mg混合粉末对土壤中多氯联苯的降解效果及其他反应条件对降解效果可能造成的影响。当金属混合粉末Fe和Mg的摩尔比为2：3,混合粉末添加量(wt)：污染土壤量(wt)=1：500,室内光及室温条件(20℃)下反应24h,污染土壤中多氯联苯的降解率达到98.10%。本研究中的降解方法还受到电解质溶液、反应时间、光照条件和温度等因素的影响。由实验结果可知,降解效率随着反应时间的延长不断提高,在反应开始的6h提高速率最快,到24h能达到98%以上；人工添加电解质溶液后,相同作用时间内获得的降解效率更高；直接光照有利于多氯联苯的降解,在反应最初的6-8h作用明显；在20℃-50℃的情况下,温度升高不利于多氯联苯的降解,20℃时,修复效果最好,降解效率为96.32%；Fe-Mg摩尔比在0.2-0.67的范围变化时,降解效率几乎没有变化；从2：3扩大到1：1时,降解率有所下降,1：1时的降解率为93.29%。
2.研究了金属Fe-Mg混合粉末对土壤中多氯联苯的降解机理。结果表明,在金属混合粉末作用下,多氯联苯脱氯降解,生成了两种新的产物：对异丙基甲苯和2,6-二(三甲基硅氧基)苯甲酸三甲基硅酯,其毒性均低于多氯联苯本身的毒性。
以上研究表明,零价金属铁镁混合粉末对多氯联苯污染土壤是一种有效的修复方法,为今后的PCBs污染土壤修复提供了较高的参考价值。
Polychlorinated biphenyl (PCB) is the most typical kind of 12 types of persistent organic pollutants (POPs) that people have always been paying attention to. Remediation of PCB-contaminated soil has been one of the hotspot researches for its extremely stable physical-chemical property. This paper has investigated the effect of zero-valent metallic mixed powder by iron and magnesium for repairing PCB-contaminated soils and has obtained good results. The main researches of the paper were as follows.
1. Investigating the degradation effect of PCB-contaminated soils by metallic mixed powder composed of iron and magnesium and reaction parameters that may have influences on removal efficiency. Removal rate of PCBs can be up to 98.10% in 24h under the conditions of Fe-Mg ration was 2:3 and power-soil ratio (wt%) was 1:500, in room with room temperature (20℃). The influences by electrolyte solution, reaction time, direct sunlight and temperature on the effect of remediation have also been studied. According to the experimental results, it can be seen that removal rate was increasing with the extension of reaction time and it could be up to 98% in 24h; addition of extra electrolyte solution could lead to better remediation effect in the same reaction time; direct sunlight has been proved to be helpful in the degradation process, especially in the first 6-8h; raising temperature was adverse to the degradation effect when temperature was ranging from 20℃to 50℃, it could get the highest removal rate 96.32% as temperature was controlled to 20℃. Ratio of Fe-Mg was ranging from 0.2-0.67 without any obvious change of removal efficiency, when it was raised from 0.67-1, removal rate has decreased and was 93.29% as the ratio was 1.
2. Investigating the mechanism of degradation. Result has indicated that two products were found after degradation process of PCBs, one was para-cymene, the other was trimethylsilyl 2,6-bis (trimethylsilyloxy) benzoate, toxicity of both were less than polychlorinated biphenyls.
Researches above demonstrated that zero-valent metallic mixed powder by iron and magnesium is an effective technique for remediation of PCB-contaminated soils and that, it provides a reference for remediation of PCB-contaminated soils in future.
引文
[1]苏丽敏,袁星.持久性有机污染物(POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9)：62-73
[2]冯文,张建阳，张鹏.持久性有机污染物(POPs)的全球污染及治理[J].质量与市场,2007
[3]陈红梅PFOS类持久性有机污染物的检测技术研究进展[J].有机氟工业,2008,(4)：53-58
[4]李宝惠.淘汰持久性有机污染物(POPs)最新进展[J].山东环境,2001,101：40-41
[5]Soliman K^L. Changes in concentration of pesticide residues in potatces during washing and home preparation [J]. Food and Chemical Toxicology,2001,39:887
[6]Weber K, Goerke H. Organochlorine compounds in fish off the Antarctic Peninsula [J]. Chemosphere,1996,33:404-410
[7]刘潇,王婷.持久性有机污染物的现状及来源分析[J].安徽农学通报,2008,14(21)：71-73
[8]齐美富,桂双林,刘俭根.持久性有机污染物(POPs)治理现状及研究进展[J].江西科学,2008,26(1)：92-96
[9]苏丽敏,袁星,赵建伟,等.持久性有机污染物(POPs)及其归趋研究[J].环境科学与技术,2003,26(5)：61-63
[10]Vallack HW, Bakker D J, Brandt I, et al. Controlling persistent organic pollutants what next? [J]. Environmental Toxicology and Pharmacology,1998, (6):143-175
[11]Segstro M, Muir D, Hobson K, et al. Are unexpectedly high levels of PCBs and other organochlorines in walrus due to predation on seals? [R]. Presented at the International Conference on Marine Mammal Biology,1993
[12]Ballschmitter K. Persistent, ecotoxic and bioaccumulating compounds and their possible environmental effects [J]. Pure and Appl. Chem.,1996,68:1771-1780
[13]赵英,赵毅,马双忱.亲核取代-热分解法破坏多氯联苯[J].华北电力大学学报.1997,24(1)：61-66
[14]阙明学.我国土壤中多氯联苯污染分布及源解析[D].哈尔滨：哈尔滨工程大学,材料科学与化学工程学院,2007
[15]张辉.土壤环境学[M].北京：化学工业出版社,2005.161
[16]Reijnders PJH. Reproductive failure in common seals feeding on fish from polluted coastal waters [J]. Nature,1986,22:147-156
[17]曹先仲,陈花果,申松海,等.多氯联苯的性质及其对环境的危害[J].中国科技论文在线,2008,3(5)：375-381
[18]苏丽敏,袁星.持久性有机污染物(POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9)：62-73
[19]Falck Jr F, Ricci Jr A, Wolff Ms, et al. Pesticides and polychlorinated biphenyl residues in human breast lipids and their relation to breast cancer [J]. Arch. Environ. Health,1992, 47:143-146
[20]BARR J R. Photolysis of polychlorinated biphenyls on octadecylsilylated silica particles [J].Chemosphere,1999,39(11):1795-1807
[21]毕新慧,徐晓白.多氯联苯的环境行为[J].化学进展,2000,12(2)：152-160
[22]郑海龙,陈杰,邓文婧.土壤环境中的多氯联苯(PCBs)及其修复技术[J].土壤(soils),2004,36(1)：16-20
[23]李法云,曲向荣,吴龙华.污染土壤生物修复理论基础与技术[M].北京：化学工业出版社,2006.116
[24]邢颖,吕永龙,刘文彬,等.中国部分水域沉积物中多氯联苯污染物的空间分布、污染评价及影响因素分析[J].环境科学,2006,27(2)：228-234
[25]葛冬梅.多氯联苯环境污染研究综述[J].甘肃科技,2007,23(9)：129-133
[26]李森,陈家军,孟占利.多氯联苯处理处置方法国内外研究进展[J].中国环保产业,2004,(2)：26-29
[27]张光明,吴敏生,张锡辉.2氯联苯与4氯联苯的超声波降解研究[J].环境化学,2004,23(3)：298-300
[28]HSU P C, FOSTER K G, FORD T D, et al. Treatment of solid wastes with molten salt oxidation [J]. Waste Management,2000,20:363-368
[29]HATAKEDA K, IKUSHIMA Y, SATO O, et al. Supercritical water oxidation of polychlorinated biphenyls using hydrogen peroxide [J]. Chemical Engineering Science, 1999,54:3079-3084
[30]LEE S H, PARK K C, MAHIKO T, et al. Supercritical water oxidation of polychlorinated biphenyls based on the redox reactions promoted by nitrate and nitrite salts [J]. The Journal of Supercritical Fluids,2006,39(1):54-62
[31]BUNCE N J, MERICA S G, LIPKOWSKI J. Prospects for the use of electrochemical methods for the destruction of aromatic organochlorine wastes [J]. Chemosphere,1997, 35:2719-2726
[32]SUN G R, HE J B, PITTMAN C U. Destruction of halogenated hydrocarbons with solvated electrons in the presence of water [J]. Chemosphere,2000,41:907-916
[33]PITTMAN C U, HE J B.Dechlorination of PCBs, CAHs, herbicides and pesticides neat and in soils at 25℃ using Na/NH3 [J]. Journal of Hazardous Materials,2002,92:51-62
[34]TANIGUCHI S, MURAKAMI A, HOSOMI M, et al. Chemical decontamination of PCB-contaminated soil [J]. Chemosphere,1997,34:1631-1637
[35]CHEN A S C, GAVASKAR A R, ALLEMAN B C, et al. Treating contaminated sediment with a two-stage base-catalyzed decomposition (BCD) process:bench-scale evaluation [J]. Journal of Hazardous Materials,1997,56:287-306
[36]Wekhof A. Treatment of contaminated water, air, and soil with UV flashlamps [J]. Environ. Progr.,1991,10:241-246
[37]Cunning ham S. D., AndersonT. A., SchwabA. P., et al. Phytoremediation of soils contaminated with organic pollutants [J]. Advances in Agronomy,1996,56(1):55-114
[38]VanceD. B. Phytoremediation:enhancing natural attunation processes [J]. National Environmental Journal,1996,6:30-31
[39]张太平,潘伟斌.根际环境与土壤污染的植物修复研究进展[J].生态环境,2003,12(1)：76-80
[40]刘晓冰,邢宝山,周克琴,等.污染土壤植物修复技术及其机理研究[J].中国生态农 业学报,2005,13(1)：134-138
[41]何娜,李培军,范淑秀,等.零价金属降解多氯联苯[J].生态学杂志,2007,26(5)：749-753
[42]Gillham R W, O'HannesinSF. ModerntrendsinHydrology [C], In:International Association of Hydrologists Conference, Hamilton, Canada,1992,10
[43]施汉昌,赵胤慧,李瑞瑞.零价金属作还原剂处理卤代有机物的研究与进展[J].给水排水,1999,25(2)
[44]Sayles G. D, You G, Wang M, Kupferle M. J. DDT, DDD, and DDE Dechlorination by Zero-valent Iron [J]. Environ. Sci. Technol.,1997,31(12):3448-3454
[45]Chuang F W, Larson R A, Wessman M S. Zero-valent iron-promoted dechlorination of polychlorinated biphenyls [J]. Environ. Sci. Technol.,1995,29(9):2460
[46]Yak HK, Lang Q, Wai CM.2000. Relative resistance of positional isomers of polychlorinated biphenyls towards reductive dechlorinaion by zero-valent iron in subcritical water [J]. Environm ental Science and Technology,2000,34 (13):2792-2798
[47]Yak HK, Wenclawiak BW, Cheng IF, et al.1999. Reductive dechlorination of polychlorinated biphenyls by zero-valent iron in subcritical water. Environm ental Science and Technology,1999,33(1):1307-1310
[48]陈宜菲.零价金属脱氯降解有机氯化污染物研究进展[J].安庆师范学院学报(自然科学版),2005,11(3)：38-42
[49]Wang, C.B., Zhang, W.X.. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs [J]. Environ. Sci.Technol.1997,31:2154-2156
[50]Patanjali Varanasi, Andres Fullana, Sukh Sidhu. Remediation of PCB contaminated soils using iron nano-particles [J]. Chemosphere,2007,66:1031-1038
[51]Grittini C, MalcomsonM, Fernando Q, et al. Rapid dechlorination of polychlorinated biphenyls on the surface of a Pd/Fe bimetallic system [J]. Environmental Science and Technology,1995,29(11):2898-2900
[52]全燮,刘会娟,杨凤林,等.二元金属体系对水中多氯有机物的催化还原脱氯特性[J].中国环境科学,1998,18(4)：333-336
[53]Chin Jung Lin, Shang Lien Lo, Ya Hsuan Liou. Dechlorination of trichloroethylene in aqueous solution by noble metal-modified iron [J]. Journal of Hazardous Materials,2004, B116:219-228
[54]Yoshiharu Mitoma, Naoyoshi Egashira, Cristian Simion. Highly effective degradation of polychlorinated biphenyls in soil mediated by a Ca/Rh bicatalytic system [J]. Chemosphere,2009,74:968-973
[55]薛荔栋,郎印海,刘爱霞,等.零价铁脱氯还原多氯联苯的研究进展[J].环境科学与技术,2009,32(3)：78-82
[56]蒋彩平Enterbacter sp. LY402生物降解土壤中多氯联苯的研究[D].大连：大连理工大学,环境生命学院,2007
[57]葛庆波,张万峰.气相色谱法测定土壤中多氯联苯[J].黑龙江环境通报,2004,28(2)：57-58
[58]李国刚.空气和土壤中持久性有机污染物监测和分析方法[M].北京：中国环境科学出版社,2008.59
[59]EPA 8082. Polychlorinated Biphenyls (PCB) by Gas Chromatography.
[60]M.A. Manzano, J.A. Perales, D. Sales. Using solar and ultraviolet light to degrade PCBs in sand and transformer oils [J]. Chemosphere,2004,57:645-654
[61]王政华,施周.利用紫外光降解多氯联苯(PCBs)的研究进展[J].环境污染治理技术与设备,2001,2(6)：10-15
[62]Simon A. Jackrnan, Christopher J. Knowles, Gary K. Robinson. SACRED-a novel catalytic process for the environmental remediation of polychlorinated biphenyls (PCBs) [J]. Chemosphere,1999,38 (8):1889-1990
[63]Shin Tanirmchi, Akihiko Murakami, Masaaki Hosomi. Chemical decontamination of PCB-contaminated soil [J]. Chemosphere,1997,34:1631-1637
[64]张辉.土壤环境学[M].北京：化学工业出版社,2005.161
[65]Li Lin, Songhu Yuan, Jing Chen. Treatment of chloramphenicol-contaminated soil by microwave radiation [J]. Chemosphere,2010,78:66-71
[66]Matheson LJ, Tratnyek PG. Reductive dehalogenation of chlorinated methanes by iron metal [J]. Environm ental Science and Technology,1994,28(12):2045-2053
[67]全燮,刘会娟,杨凤林,等.二元金属体系对水中多氯有机物的催化还原脱氯特性[J].中国环境科学,1998,18(4)：333-336
[2]冯文,张建阳，张鹏.持久性有机污染物(POPs)的全球污染及治理[J].质量与市场,2007
[3]陈红梅PFOS类持久性有机污染物的检测技术研究进展[J].有机氟工业,2008,(4)：53-58
[4]李宝惠.淘汰持久性有机污染物(POPs)最新进展[J].山东环境,2001,101：40-41
[5]Soliman K^L. Changes in concentration of pesticide residues in potatces during washing and home preparation [J]. Food and Chemical Toxicology,2001,39:887
[6]Weber K, Goerke H. Organochlorine compounds in fish off the Antarctic Peninsula [J]. Chemosphere,1996,33:404-410
[7]刘潇,王婷.持久性有机污染物的现状及来源分析[J].安徽农学通报,2008,14(21)：71-73
[8]齐美富,桂双林,刘俭根.持久性有机污染物(POPs)治理现状及研究进展[J].江西科学,2008,26(1)：92-96
[9]苏丽敏,袁星,赵建伟,等.持久性有机污染物(POPs)及其归趋研究[J].环境科学与技术,2003,26(5)：61-63
[10]Vallack HW, Bakker D J, Brandt I, et al. Controlling persistent organic pollutants what next? [J]. Environmental Toxicology and Pharmacology,1998, (6):143-175
[11]Segstro M, Muir D, Hobson K, et al. Are unexpectedly high levels of PCBs and other organochlorines in walrus due to predation on seals? [R]. Presented at the International Conference on Marine Mammal Biology,1993
[12]Ballschmitter K. Persistent, ecotoxic and bioaccumulating compounds and their possible environmental effects [J]. Pure and Appl. Chem.,1996,68:1771-1780
[13]赵英,赵毅,马双忱.亲核取代-热分解法破坏多氯联苯[J].华北电力大学学报.1997,24(1)：61-66
[14]阙明学.我国土壤中多氯联苯污染分布及源解析[D].哈尔滨：哈尔滨工程大学,材料科学与化学工程学院,2007
[15]张辉.土壤环境学[M].北京：化学工业出版社,2005.161
[16]Reijnders PJH. Reproductive failure in common seals feeding on fish from polluted coastal waters [J]. Nature,1986,22:147-156
[17]曹先仲,陈花果,申松海,等.多氯联苯的性质及其对环境的危害[J].中国科技论文在线,2008,3(5)：375-381
[18]苏丽敏,袁星.持久性有机污染物(POPs)及其生态毒性的研究现状与展望[J].重庆环境科学,2003,25(9)：62-73
[19]Falck Jr F, Ricci Jr A, Wolff Ms, et al. Pesticides and polychlorinated biphenyl residues in human breast lipids and their relation to breast cancer [J]. Arch. Environ. Health,1992, 47:143-146
[20]BARR J R. Photolysis of polychlorinated biphenyls on octadecylsilylated silica particles [J].Chemosphere,1999,39(11):1795-1807
[21]毕新慧,徐晓白.多氯联苯的环境行为[J].化学进展,2000,12(2)：152-160
[22]郑海龙,陈杰,邓文婧.土壤环境中的多氯联苯(PCBs)及其修复技术[J].土壤(soils),2004,36(1)：16-20
[23]李法云,曲向荣,吴龙华.污染土壤生物修复理论基础与技术[M].北京：化学工业出版社,2006.116
[24]邢颖,吕永龙,刘文彬,等.中国部分水域沉积物中多氯联苯污染物的空间分布、污染评价及影响因素分析[J].环境科学,2006,27(2)：228-234
[25]葛冬梅.多氯联苯环境污染研究综述[J].甘肃科技,2007,23(9)：129-133
[26]李森,陈家军,孟占利.多氯联苯处理处置方法国内外研究进展[J].中国环保产业,2004,(2)：26-29
[27]张光明,吴敏生,张锡辉.2氯联苯与4氯联苯的超声波降解研究[J].环境化学,2004,23(3)：298-300
[28]HSU P C, FOSTER K G, FORD T D, et al. Treatment of solid wastes with molten salt oxidation [J]. Waste Management,2000,20:363-368
[29]HATAKEDA K, IKUSHIMA Y, SATO O, et al. Supercritical water oxidation of polychlorinated biphenyls using hydrogen peroxide [J]. Chemical Engineering Science, 1999,54:3079-3084
[30]LEE S H, PARK K C, MAHIKO T, et al. Supercritical water oxidation of polychlorinated biphenyls based on the redox reactions promoted by nitrate and nitrite salts [J]. The Journal of Supercritical Fluids,2006,39(1):54-62
[31]BUNCE N J, MERICA S G, LIPKOWSKI J. Prospects for the use of electrochemical methods for the destruction of aromatic organochlorine wastes [J]. Chemosphere,1997, 35:2719-2726
[32]SUN G R, HE J B, PITTMAN C U. Destruction of halogenated hydrocarbons with solvated electrons in the presence of water [J]. Chemosphere,2000,41:907-916
[33]PITTMAN C U, HE J B.Dechlorination of PCBs, CAHs, herbicides and pesticides neat and in soils at 25℃ using Na/NH3 [J]. Journal of Hazardous Materials,2002,92:51-62
[34]TANIGUCHI S, MURAKAMI A, HOSOMI M, et al. Chemical decontamination of PCB-contaminated soil [J]. Chemosphere,1997,34:1631-1637
[35]CHEN A S C, GAVASKAR A R, ALLEMAN B C, et al. Treating contaminated sediment with a two-stage base-catalyzed decomposition (BCD) process:bench-scale evaluation [J]. Journal of Hazardous Materials,1997,56:287-306
[36]Wekhof A. Treatment of contaminated water, air, and soil with UV flashlamps [J]. Environ. Progr.,1991,10:241-246
[37]Cunning ham S. D., AndersonT. A., SchwabA. P., et al. Phytoremediation of soils contaminated with organic pollutants [J]. Advances in Agronomy,1996,56(1):55-114
[38]VanceD. B. Phytoremediation:enhancing natural attunation processes [J]. National Environmental Journal,1996,6:30-31
[39]张太平,潘伟斌.根际环境与土壤污染的植物修复研究进展[J].生态环境,2003,12(1)：76-80
[40]刘晓冰,邢宝山,周克琴,等.污染土壤植物修复技术及其机理研究[J].中国生态农 业学报,2005,13(1)：134-138
[41]何娜,李培军,范淑秀,等.零价金属降解多氯联苯[J].生态学杂志,2007,26(5)：749-753
[42]Gillham R W, O'HannesinSF. ModerntrendsinHydrology [C], In:International Association of Hydrologists Conference, Hamilton, Canada,1992,10
[43]施汉昌,赵胤慧,李瑞瑞.零价金属作还原剂处理卤代有机物的研究与进展[J].给水排水,1999,25(2)
[44]Sayles G. D, You G, Wang M, Kupferle M. J. DDT, DDD, and DDE Dechlorination by Zero-valent Iron [J]. Environ. Sci. Technol.,1997,31(12):3448-3454
[45]Chuang F W, Larson R A, Wessman M S. Zero-valent iron-promoted dechlorination of polychlorinated biphenyls [J]. Environ. Sci. Technol.,1995,29(9):2460
[46]Yak HK, Lang Q, Wai CM.2000. Relative resistance of positional isomers of polychlorinated biphenyls towards reductive dechlorinaion by zero-valent iron in subcritical water [J]. Environm ental Science and Technology,2000,34 (13):2792-2798
[47]Yak HK, Wenclawiak BW, Cheng IF, et al.1999. Reductive dechlorination of polychlorinated biphenyls by zero-valent iron in subcritical water. Environm ental Science and Technology,1999,33(1):1307-1310
[48]陈宜菲.零价金属脱氯降解有机氯化污染物研究进展[J].安庆师范学院学报(自然科学版),2005,11(3)：38-42
[49]Wang, C.B., Zhang, W.X.. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs [J]. Environ. Sci.Technol.1997,31:2154-2156
[50]Patanjali Varanasi, Andres Fullana, Sukh Sidhu. Remediation of PCB contaminated soils using iron nano-particles [J]. Chemosphere,2007,66:1031-1038
[51]Grittini C, MalcomsonM, Fernando Q, et al. Rapid dechlorination of polychlorinated biphenyls on the surface of a Pd/Fe bimetallic system [J]. Environmental Science and Technology,1995,29(11):2898-2900
[52]全燮,刘会娟,杨凤林,等.二元金属体系对水中多氯有机物的催化还原脱氯特性[J].中国环境科学,1998,18(4)：333-336
[53]Chin Jung Lin, Shang Lien Lo, Ya Hsuan Liou. Dechlorination of trichloroethylene in aqueous solution by noble metal-modified iron [J]. Journal of Hazardous Materials,2004, B116:219-228
[54]Yoshiharu Mitoma, Naoyoshi Egashira, Cristian Simion. Highly effective degradation of polychlorinated biphenyls in soil mediated by a Ca/Rh bicatalytic system [J]. Chemosphere,2009,74:968-973
[55]薛荔栋,郎印海,刘爱霞,等.零价铁脱氯还原多氯联苯的研究进展[J].环境科学与技术,2009,32(3)：78-82
[56]蒋彩平Enterbacter sp. LY402生物降解土壤中多氯联苯的研究[D].大连：大连理工大学,环境生命学院,2007
[57]葛庆波,张万峰.气相色谱法测定土壤中多氯联苯[J].黑龙江环境通报,2004,28(2)：57-58
[58]李国刚.空气和土壤中持久性有机污染物监测和分析方法[M].北京：中国环境科学出版社,2008.59
[59]EPA 8082. Polychlorinated Biphenyls (PCB) by Gas Chromatography.
[60]M.A. Manzano, J.A. Perales, D. Sales. Using solar and ultraviolet light to degrade PCBs in sand and transformer oils [J]. Chemosphere,2004,57:645-654
[61]王政华,施周.利用紫外光降解多氯联苯(PCBs)的研究进展[J].环境污染治理技术与设备,2001,2(6)：10-15
[62]Simon A. Jackrnan, Christopher J. Knowles, Gary K. Robinson. SACRED-a novel catalytic process for the environmental remediation of polychlorinated biphenyls (PCBs) [J]. Chemosphere,1999,38 (8):1889-1990
[63]Shin Tanirmchi, Akihiko Murakami, Masaaki Hosomi. Chemical decontamination of PCB-contaminated soil [J]. Chemosphere,1997,34:1631-1637
[64]张辉.土壤环境学[M].北京：化学工业出版社,2005.161
[65]Li Lin, Songhu Yuan, Jing Chen. Treatment of chloramphenicol-contaminated soil by microwave radiation [J]. Chemosphere,2010,78:66-71
[66]Matheson LJ, Tratnyek PG. Reductive dehalogenation of chlorinated methanes by iron metal [J]. Environm ental Science and Technology,1994,28(12):2045-2053
[67]全燮,刘会娟,杨凤林,等.二元金属体系对水中多氯有机物的催化还原脱氯特性[J].中国环境科学,1998,18(4)：333-336